Antistain agents for spectrally sensitized silver halide photographic elements



United States Patent 3,380,828 ANl-"lSTAlN AGENTS l -{ER SPEEITRALLY SEN- SILVER EALEDE PHGTGQAAPHIC Theodore L'. Iitze, 3L, and William ltosecrants, in, Rochester, N.Y., assiguors to Eastman Kodak (Zcmpany, Rochester, N31, a corporation of New .lersey No Drawing. Aug. 2, H65, Ser. No. 476,638 29 Liaims. (ill. %51

This invention concerns spectrally sensitized photographic elements for use in rapid processing systems.

Normal photographic processing of conventional silver halide materials after exposure includes the essential steps of developing, fixing, washing, and drying in order to obtain a stable image. However, these steps require a considerable amount of time in order to obtain satisfactory quality.

In order to avoid the time-consuming steps in conventional processing, rapid processing systems have been evolved which either dispense with some of the steps or modify the steps so that they require a reduced amount of time. For instance, incorporation of the developer in the silver halide emulsion or in a layer adjacent, and/ or the use of an unhardencd emulsion increases the speed with which the exposed silver halide emulsion can be develops After development, the remaining undeveloped silver halide can be complexed with a suitable coinplexing agent to render it sufiicently stable so that it can be allowed to remain in the emulsion without requiring a washing step.

When unhardened emulsions are used, they are subject to abrasion, etc., so that it is desirable to use a hardening developer. Developers of this type have, in some instances, had poor stability since their effective hardening action tends to decrease rapidly with age. However, this problem or" stability may be avoided by incorporating in the photographic element a hardener-precursor which releases a hardener at the alkaline pH utilized for development of the exposed element,

The rapid processing systems have been panticularly useful in many applications but, in some instances, there has been a problem of stain in the non-image background area of processed prints, particularly when these have been processed by surface application of the processing agents without subsequent removal by washing or the like. This stain has been particularly evident when used with developer-containing, unhardened silver halide emulsions. Accordingly, it has been desirable to find a method of preserving the rapid processing characteristics of the silver halide elements prepared for this type of processing and reduce or eliminate the tendency to stain resulting from the presence of residual processing agents imbibed into the silver halide emulsion.

We have found that spectrally sensitized photographic elements processed using a rapid processing system exhibit little or no stain when processed in the presence of 1,3- dihydroxy carbocyclic compounds. We have also found that the use of these compounds improves the image tone of the resulting prints.

One object of this invention is to provide radiation sensitive, i.e. sensitive to light, X-rays, 7 rays, heat, etc., spectrally sensitized silver halide photographic elements containin at least one incorporated silver halide developing agent, having low strain propensity and good image tone when the exposed element is processed in a rapid processing system. Another object is to provide unhardened spectrally sensitized silver halide elements which contain at least one incorporated silver halide developing agent and having low-stain propensity and good image tone.

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Another object is to provide unhardened spectrally sensitized silver halide elements which contain at least one incorporated silver halide developing agent and a hardener precursor and having low stain propensity and good image tone when the exposed element is processed in a rapid processing system.

A further object is to provide unhardened spectrally sensitized silver halide elements which contain at least one incorporated silver halide developing agent, a hardener-precursor, a carbocyclic 1,3-dione stabilizer and a rapid stabilization processing anti-stain agent which is a 1,3-dihydroxy compound. Other objects will be evident from the following disclosur In one embodiment of our invention, an unhardened silver halide emulsion is prepared using a colloid binder such as gelatin, a hardene -precursor, and containing an incorporated developer, such as hydroquinone, etc. The silver halide emulsion, coated on a suitable support, such as paper, also contains a carbocyclic 1,3-dione such as,

for example, 5,5dimethyl cyclohexane-l,3-dione and a l,3-dihydroxy carbocyclic antistain agent, such as, for example, l,3,5-trihydroxybenzene. After the emulsion is exposed to a light image, it is developed by imbibing into the surface aqueous alkaline solution which activates the developer to form a silver image. The silver halide emulsion is then passed through a stabilizing bath containing a silver halide complexing agent such as ammonium thiosulrate. The incorporation of the antistain agents prevents the formation of background stain.

In carrying out our invention, the photographic element contains, a 1,3-dihydroxy carbocyclic compound provided the compound does not have hydroxyl groups in adjacent positions, such as in the 1,2-positions.

Typical suitable carbocyclic l,3-dihydroxy compounds include those having the formula:

wherein R may be lower alkyl, substituted lower alkyl, halogen, hydrogen, etc., provided it is not hydroxy and Z represents e atoms required to complete a carbocyclic ring, e.g., having 5 to 6 carbons in the nucleus as cyclopentane, cyclohexane, cyclopentene, cycloliexene, etc., such that the ring may be unsubstituted or substituted with groups, such as an allcyl (e.g., methyl, ethyl, butyl, hexyl, etc); an aryl, (e.g., phenyl, tolyl, methoxyphenyl, hexadecyloxyphenyl, naphthyl, etc); cyano; a carbalkoxy (e.g., carbomethozy, carboethoxy, carbobutoxy, etc.), etc., free bonds being satisfied by hydrogen and the dotted lines representing carbon to carbon bonds when the carbocyclic ring is unsaturated.

Especially useful 1,3-dihydroxy compounds include those illustrated by the following formula:

ethyl, carooxymethyl, etc., halogen, hydrogen, etc., provided R is not hydroxy, R represents a group selected from the class consisting of hydrogen; halogen, an alkyl (e.g., methyl, ethyl, butyl, etc.); an aryl (e.g., phenyl, tolyl, naphthyl, etc); cyano; a carballroxy (e.g., carbomethoxy, carboethoxy, etc.); and R is selected from the class consisting of hydrogen; hydroxy; an alkyl (e.g., methyl, ethyl, butyl, amyl, etc.) an aryl (e.g., phenyl, me'thoxyphenyl, ethoxyphenyl, hexadecyloxyphenyl, tolyl, naphthyl, etc.). R and R may be united to form an aromatic ring.

Typical examples of compounds included in Formula I that are used to advantage according to our invention are:

( 1 1,3-dihydroxy-5,5-dimethylcyclohexane (2) i 1,3-dihydroxy-cyclohexane (3) l,3-dihydroxy-4,G-dicyano-S,S-dimethylcyclohexane (4) 1,3-dihydroxy-cyclopentane (5) 1,3-dihydroxy-4,4-dimethylcyclopentane The compounds of Formula I may be added to the un hardened layers at a concentration of about 0.005 to 1 mole/mole silver.

Although we prefer the use of substituted or unsubstituted 1,3-dihydroxy benzenes, We also regard the cognate naphthalene analogues within the scope of our invention where they do not introduce objectionable light absorption,

The spectrally-sensitized photographic elements of our invention may contain, along with the 1,3-dihydroxy carbocyclic antistain agents, a carbocyclic 1,3-dione stabilizer, a hardener precursor, inert solid particles, and other addenda.

Typical suitable carbocyclic 1,3-diones include those having the formula:

wherein Z represents the atoms required to complete a carbocyclic ring, e.g., having 5 t 6 carbons in the nucleus as cyclopen-tane, cyclohexane, cyclopentene, cyclohexene, etc., such that the ring may be unsubstituted or substituted with groups, such as an alkyl (e.g., methyl, ethyl, butyl, hexyl, etc.); an aryl, (e.g., phenyl, tolyl, methoxyphenyl, hexadecyloxyphenyl, naphthyl, etc.); cyano; a carbalkoxy, (e.g., carbomethoxy, carboethoxy, carbobutoxy, etc.), etc. They may be incorporated in an amount of 0.05 to 1 mole/mole silver.

Particularly useful hardener precursors are aldehyde hardener precursors such as aldehyde bisulfite addition products, methylol derivatives and other aldehyde releasing compounds. Aldehyde releasing compounds of variot'ls types may be used. Typical compounds are described in Allen and Burness British Patent 825,544; Baldsiefen US. Patent 2,364,017; Orkin US. Patent 2,494,055; Harriman US. Patent 2,591,542; Schwartz U.S. Patent 2,599,518; British Patent 676,628 and British Patent 749,326.

The hardener precursors are added to the unhardened layers in the photographic element at a concentration of about -35 and preferably between and based on the total amount of vehicle in the unhardened layers.

The above addenda' may be incorporated directly into the silver halide layer and/or into a layer contiguous thereto.

The inert particles employed are water insoluble, solid particles and have a diameter in the range of about 7 to about 15 microns, preferably about 8 to about 12 microns and include any of the water insoluble particulate organic or inorganic compounds which can be used to provide the photographic element with the required surface characteristics. Examples of suitable inert particles include starch, barium sulfate, calcium carbonate, cellulose esters such as celluolse acetate propionate, cellulose others such as ethyl cellulose, synthetic resins such as polymeric esters of acrylic and methacrylic acid, as exemplified by polymethyl methacrylate, polyvinyl resins such as polyvinyl acetate and polyvinyl alcohol, polycarbonates, homo and copolymers of styrene, organic oxides such as zinc oxide, silica, glass, titanium dioxide, magnesium oxide and aluminum oxide, as well as hardened gelatin grains, calcium sulfate, barium carbonate and the like.

The discrete particles can be incorporated into one or more layers on an emulsion side surface of a support in a photographic element. These particles are incorporated into at least one layer which is no farther from the support than the emulsion layer, i.e., they are incorporated in the photographic silver halide emulsion layer and/or a layer lying between said emulsion layer and the support. The in rt particles can also be put into both the photographic silver halide emulsion layer and an adjacent layer. The solid inert particles are incorporated into the photographic element of this invention using any method which will achieve uniform dispersion of the particles in ne or more layers of the element. For example, the inert particles are not light-sensitive and can be dispersed directly in a photographic silver halide coating solution or they can be dispersed in an aqueous solution or dispersion of the silver halide binding agent, which solution is mixed with a photo-graphic silver halide emulsion prior to coating the latter to form a light-sensitive layer. In general, the solid inert particles are present in the photographic element in concentrations in the range of about 20 to about 150, preferably about 30 to about 100 mg./ft. of support.

Various colloids can be used as vehices or binding agents in the photographic elements of this invention. Among such agents are gelatin, or other colloidal materials such as colloidal albumin, cellulose derivatives, synthetic resins such as polyvinyl compounds, acrylamide polymers or the like. It is often advantageous to employ combinations or" binding agents. Suitable combinations include mixtures of gelatin with aqueous dispersions of polymerized ethylenically unsaturated compounds. The binding agents, particularly gelatin, are usually coated at coverages in the range of about 50 to about 1000, preferably about 50 mg. to about 300 mg./ft. of support.

The silver halides employed in the preparation of the light-sensitive coatings described herein include any of the photographic silver halides, as exemplified by silver bromide, silver iodide, silver chloride or mixed silver halides such as silver chlorobromide or silver bromoiodide. These photographic silver halides can be coated at silver coverages of about 30 to about 150, preferably 45 to about mg/ft. of support. The silver halides used in the photographic elements of this invention may be those which form latent images predominantly on the surface of the silver halide grains or those which form latent images predominantly inside the silver halide crystals, such as those described in Davey and Knott US. Patent 2,592,250. The silver halide emulsions may be developing out emulsions or direct print emulsions which sometimes also are developed as described in French Patents 1,368,647 and 1,329,911 and Fix US. application 338,605, filed Jan. 20, 1964, now Patent 3,326,689.

The photographic layers described herein can be superimposed upon a wide variety of supports. Typical flexible supports include those generally employed for photographic elements such as cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film and related films or resinous materials as well as very thin glass, film, paper, and the like. Supports such as paper which are partially aCetylated or coated with baryta or an a-olefin polymer, particularly a polymer of an a-olefin containing 2-10 carbon atoms as exemplified by polyethylene, polypropylene, ethylene butene copolymers and the like, can also be'employed.

The photographic elements of this invention can also contain additional addenda, particularly those known to be beneficial in one or more layers of a photographic element. For example, these elements can contain stabilizers or antifog ants such as organic azoles, azaindenes, mercaptans, metal salts such as cadmium, lead, mercury, gold, or other noble metal salts, spectral sensitizers such as the cyanines, merocyanines, complex (trinuclear) cyanines, complex (trinuclear) merocyanines, styryls, hemicyanines, etc., speed increasing materials, such as polyalkylene glycols, onium salts, thioethers, gelatin hardeners, plasticizers, coating aids such as anionic, non-ionic and amphoteric surface active compounds, and the like. The photographic silver halide emul sions can also be chemically sensitized with compounds of the sulfur group such as sulfur, selenium and tellurium sensitizers, noble metal salts such as gold, or reduction sensitized with reducing agents or combinations of such materials. The photographic elements can contain fluorescent brighteners such as stilbenes, coumarins, benzothiazoles, benzoxazoles, imidazoles, etc. Suitable iluoroescent brighteners are described in McEall et al., US. Patent 2,933,390; Geigy, British Patent 786,234; Seyler, US. Patent 3,025,242 and Leonar-Werke, German Patent 1,150,274.

The invention can be further illustrated by the followiug examples of preferred embodiments thereof although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention.

Example 1 A paper support which contained to hardeners was coated with a gelatin solution to yield the followingcoverages per square foot: gelatin, 220 mg; 1,3-cyclohexanedione, 16 mg; gluteraldehyde bis-bisulfite, 55 m 1-phenyl-3-pyrazolidone, 16 mg; hydroquinone, 62 m Two samples of this coating were then overcoated with photographic emulsions as follows:

Sample I was overcoated with an unhardened silver brornoiodide emulsion, green sensitized with a merocyanine dye of the type described in US. Patent 2,493,- 748, at a silver coverage of 180 mg./ft. and a gelatin coverage of 260 mg./ft. This sample served as a control.

Sample 11 was overcoated with a similar emulsion under identical conditions and differed only in that is contained, also, 61 millimoles of 1,3,5-trihydroxy benzene per silver mole.

These coating samples were exposed to a tungsten light source to yield a density of 0.6 when processed through an activator solution (containing per liter 70 grams of potassium hydroxide, 40 grams of sodium bisulfide and 2.0 grams of potassium bromide) for 2.6 seconds at 70 F., and then through a stabilizer solution (containing per liter 300 grams of ammonium thiocyanate, 40 grams of sodium bisulfide, grams of sodium thiosulfate pentahydrate and 15 grams of monobasic sodium phosphate) for 3.0 seconds in a two-stage rapid access processor.

The stabilized prints were examined for background stain and image tone to yield the following results:

Sample Image Tone Background Stain I Brown High. II Neutral Low.

Example 2 Image Tone Background Stain High. Low.

Example 3 Sample I-No addition (control) Sample 11-1,3,5-trihydroxybenzene Sample ill-1,3-dihydroxybenzene Sample lV4-chloro-1,3-dihydroxybenzene Sample V1,2,3-trihydroxybenzene Upon exposure and processing as descrcibed in Example 1, the following evaluation was made of background stain and of image tone:

Sample Image Tone Background Stain I Brown Medium II. Neutral Low. III- Gray-brown to neutral.. Medium. IV. Neutral Low. V Brown Medium.

Example 4 Although the 1,3-dihydroxy carbocyclic compounds of our invention produce the greatest improvements in elements containing unhardened silver halide emulsion layers, they may also be used to advantage with hardened silver halide emulsion layers as illustrated by this example.

A hardened gelatin-silver chloride emulsion spectrally sensitized with a merocyanine dye was coated as a single layer on a paper support to yield the following coverages per square foot: silver, 120 mg; gelatin, 320 mg; hydroquinone, mg; and l-phenyl-B-pyrazolidone, 2.4 mg. This coating, which served as a control, was designated Sample I.

A similar coating, Sample 11, was prepared which differed from Sample I only in that it contained also 19.5 millimoles of 1,3,5-trihydroxybenzene.

When these two samples were tested as described in Example 1, the following results were obtained.

Sample: Background stain I (control) High. 11 LOW.

Thus, Sample II exhibited a significant reduction in stain relative to Sample I.

The advantages of the rapid access stabilization process and in particular the use of our elements containing certain 1,3-dihydroxy carbocyclic compounds to act as antistain and toning agents therein are thus readily apparent.

One of the chief advantages 'lies in the fact that the usual developing solution containing developing agent is dispensed with. As is well known, the usual developing solutions have a very short life partly because the developing agent therein readily oxidized in the presence of air even when restrainers are incorporated in the developer. Therefore, the worker must continually change developing solutions. Since We incorporate the developing agent into the emulsion layer, there is no need to use a developing agent in the alkaline treating solution although this can be done if desired. Also, with the elimination of the usual washing step, the total processing time for a print has been decreased, yet the prints obtained by the use of the elements of our invention are found to be substantialiy free of stain and to possess good image tone even though they are unwashed.

The developing agents may be incorporated into emulslons of types other than shown in the above examples; for example, the well-known direct positive type of emulsion, particularly those disclosed in the Kendall et al. U.S. patent application Ser. No. 35,987, filed June 29, 1948, now Patent No. 2,541,472, issued Feb. 13, 1951, may contain the developing agent and be processed in a manner similar to that described in the above examples. The result, of course, is to obtain a direct positive stabilized image from the original copy.

The emulsions of our invention are preferably gelatino-silver halide emulsions. However, they are not limited thereto since other water-permeable organic colloid vehicles may be used for dispersing the silver salt and developing agent, e.g., polyvinyl alcohol, partially hydrolyzed polyvinyl esters and cellulose esters, etc.

The developing agents useful in emulsions processed according to our invention include, for example, conventional silver halide developing agents such as hydroquinones, S-pyrazolidones, p-aminophenols, etc. as well as precursors thereof. Combinations of these developer agents may also be utilized. The concentrations of silver halide developing agents in our emulsions may be varied over a Wide range. The amount selected will normally be based on the ability to provide images of adequate density as well as providing an emulsion having optimum keeping properties.

The silver halide stabilizing agents mentioned above may be used as in the above examples in an aqueous solution, but it is advantageous to make the stabilization bath acidic to counteract alkali present in the developing solution. The alkali of the developing solution is not especially critical since carbonate caustic alkali and borates all give useful results, although strong alkali is preferred in the alkaline treating solution since it will increase the rate of development.

Although the photographic elements of our invention may be immersed in the alkaline and stabilizing solutions, we prefer merely to moisten the surface of the exposed elements with these solutions. Thus, in the case of paper supports, the support does not become excessively wet and the drying time is thereby greatly reduced or even eliminated.

It will be apparent from the foregoing description of our invention that a substantial proportion of the silver compounds remains in the emulsion after the stabilizing treatment. This difiers from the customary fixing and washing in which the intent is to remove the residual silver halide from the emulsion.

It will be understood that the examples and modifications described herein are illustrative only and that our invention is to be taken as limited only by the scope of the appended claims.

We claim:

1. A radiation-sensitive photographic element comprising a support having thereon a spectrally-sensitized silver halide photographic emulsion layer, a silver halide developing agent and a l,3dihydroxy carbocyclic compound antistain agent.

2. A light-sensitive photographic element comprising a support having thereon a spectrally-sensitized unhardened silve halide photographic emulsion layer, a silver hdide developin agent and a 1,3-dihydroxy carbocyclic compound antistain agent.

3. A light-sensitive photographic element comprising a support having thereon a spectrally-sensitized silver halide photographic emulsion layer, a silver halide developing agent and a 1,3-dihydroxybenzene.

4. A light-sensitive photographic element comprising a support having thereon a spectrally-sensitized unhardened silver halide photographic emulsion layer, a silver halide developing agent, and a 1,3-dihydroxybenzene.

5. A light-sensitive photographic element comprising a support having thereon a spectrally-sensitized silver halide photographic emulsion layer, a silver halide developing agent, a carbocyclic 1,3-dione stabilizer, and a 1,3- dihydroxy carbocyclic compound antistain agent.

6. A light-sensitive photographic element comprising a support having thereon a spectrally-sensitized unhardened silver halide photographic emulsion layer, a silver halide developing agent, a carbocyclic 1,3-dione stabilizer, and a 1,3-dihydroxy carbocyclic compound antistain agent.

7. A light-sensitive photographic element comprising a support having thereon a spectrally-sensitized unhardened silver halide photographic emulsion layer, a silver halide developing agent, a hardener precursor, and a 1,3- dihydroxy carbocyclic compound antistain agent.

3. A light-sensitive photographic element comprising a support having thereon a spectrally-sensitized unhardened silver halide photographic emulsion layer, a silver halide developing agent, a hardener precursor, a carbocyclic 1,3-dione stabilizer, and a 1,3-dihydroxy carbocyclic compound antistain agent.

9. A lightsensitive photographic element comprising a support having thereon a spectrally-sensitized unhardened silver halide photographic emulsion layer, a combination of hydroquinone and 3-pyrazolidone silver halide developing agents, and a 1,3-dihydroxy carbocyclic compound antistain agent.

it A- light-sensitive photographic element comprising a support having thereon a spectrally-sensitized unhardened silver halide photographic emulsion layer, a silver halide developing agent, water insoluble particulate material, and a 1,3-dihydroxy carbocyclic compound antistain agent.

11. A light-sensitive photographic element comprising a support having thereon a spectrally-sensitized unhardened silver halide photographic emulsion layer, a silver halide developing agent, 5,5-dimethyl cyclohexane-1,3- dione and 1,3,5-trihydroxy benzene.

12. A light-sensitive photographic element comprising a support having thereon a spectrally-sensitized unhardened silver halide photographic emulsion layer, a silver halide developing agent and 1,3,5-trihydroxybenzene.

13. A light-sensitive photographic element comprising a support having thereon a spectrally-sensitized unhardened silver halide photographic emulsion layer, a silver halide developing agent, and 4-chloro-1,3-dihydroxybenzene.

1 A rapid access stabilization process for the formation of a stable image in a photographic silver halide material which comprises developing an exposed silver halide photographic element comprising a support having thereon a spectrally-sensitized silver halide emulsion, at least one silver halide developing agent, and a 1,3-dihydroxy carbocyclic compound antistain agent, by treatment with an alkaline solution, and immediately thereafter stabilizing said emulsion with a solution comprising at least one compound selected from the group consisting of alkali metal, alkaline earth and ammonium thiocyanates and thiosulfates, thioureas and thioglycollic acid, and drying said element without further treatment.

15. A rapid access stabilization process for the formation of a stable image in a photographic silver halide material which comprises developing an exposed silver halide photographic element comprising a support having thereon a spectrally-sensitized silver halide emulsion, a combination of hydroquinone and 3-pyrazolidone silver halide developing agents, and a 1,3-dihydroxy carbocyclic compound antistain agent, by treatment with an alkaline solution and immediately thereafter stabilizing said emulsion with a solution comprising at least one compound selected from the group consisting of alkali metal, alkaline earth and ammonium thiocyanates and thiosulfates, thioureas and thioglycollic acid, and drying said element without further treatment.

16. A rapid access stabilization process for the formation of a stable image in a photographic silver halide material which comprises developing an exposed silver halide photographic element comprising a support having thereon an unhardened spectrally-sensitized silver halide emulsion, at least one silver halide developing agent, a

hardener precursor, a carbocyclic 1,3-dione stabilizer, Water insoluble particulate material, and a 1,3-dihydroxy carbocyclic compound, by treatment with an alkaline solution, and immediately thereafter stabilizing said emulsion with a solution comprising at least one compound selected from the group consisting of alkali metal, alkaline earth and ammonium thiocyanates and thiosulfates, thioureas and thioglycollic acid, and drying said element without further treatment.

17. A rapid access stabilization process for the formation of a stable image in a photographic silver halide material which comprises developing an exposed silver halide photographic element comprising a support having thereon an unhardened spectrally-sensitized silver halide emulsion, at least one silver halide developing agent, a carbocyclic 1,3-dione, a hardener precursor, and a 1,3- dihydroxy carbocyclic compound, by treatment with an alkaline solution, and immediately thereafter stabilizing said emulsion with a solution comprising at least one compound selected from the group consisting of alkali metal, alkaline earth and ammonium thiocyanates and thiosulfates, thioureas and thioglycollic acid, and drying said emulsion without further treatment.

18. A rapid access stabilization process for the formation of a stable image in a photographic silver halide material which comprises developing an exposed silver halide photographic element comprising a support having thereon an unhardened spectrally-sensitized silver halide emulsion, at least one silver halide developing agent, and l,3dihydroxybenzene, by treatment with an alkaline solution, and immediately thereafter stabilizing said emulsion with a solution comprising at least one compound selected from the group consisting of alkali metal, alkaline earth and ammonium thiocyanates and thiosulfate's, thioureas and thioglycollic acid, and drying said element Without further treatment.

19. A rapid access stabilization process for the formation of a stable image in a photographic silver halide material which comprises developing an unexposed silver halide photographic element comprising a support having thereon a spectrally-sensitized silver halide emulsion, at least one silver halide developing agent, and 1,3,5-trihydroxy-benzene, by treatment with an alkaline solution, and immediately thereafter stabilizing said emulsion with a solution comprising at least one compound selected from the group consisting of alkali metal, alkaline earth and ammonium thiocyanates and thiosulfates, thioureas and thioglycollic acid, and drying said emulsion Without further treatment.

20. A rapid access stabilization process for the formation of a stable image in a photographic silver halide material which comprises developing an unhardened silver halide photographic element comprising a support having thereon a spectrally-sensitized silver halide emulsion, at least one silver halide developing agent, and 4-chloro- 1,3-dihydroxybenzene, by treatment with an alkaline solution, and immediately thereafter stabilizing said emulsion with a solution comprising at least one compound selected from the group consisting of alkali metal, alkaline earth and ammonium thiocyanates and thiosulfates, thioureas and thioglycollic acid, and drying said element Without further treatment.

References Cited FOREIGN PATENTS 4/1963 Belgium.

OTHER REFERENCES Chemical Abstract 61:1427h.

NORMAN G. TORCHIN, Primary Examiner.

C. E. DAVIS, Assistant Examiner. 

14. A RAPID ACCESS STABILIZATION PROCESS FOR THE FORMATION OF A STABLE IMAGE IN A PHOTOGRAPHIC SILVER HALIDE MATERIAL WHICH COMPRISES DEVELOPING AN EXPOSED SILVER HALIDE PHOTOGRAPHIC ELEMENT COMPRISING A SUPPORT HAVING THEREON A SPECTRALLY-SENSITIZED SILVER HALIDE EMULSION, AT LEAST ONE SILVER HALIDE DEVELOPING AGENT, AND A 1,3-DIHYDROXY CARBOCYLIC COMPOUND ANTISTAIN AGENT, BY TREATMENT WITH AN ALKALINE SOLUTION, AND IMMEDIATELY THEREAFTER STABILIZING SAID EMULSION WITH A SOLUTION COMPRISING AT LEAST ONE COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL, ALKALINE EARTH AND AMMONIUM THIOCYANATES AND THIOSULFATES, THIOUREAS AND THIOGLYCOLLIC ACID AND DRYING SAID ELEMENT WITHOUT FURTHER TREATMENT. 